Polyamideimides

ABSTRACT

New and useful polyamideimides and their precursor polyamic acids are provided. The polyamic acid is prepared by reacting aliphatic diacid, tricarboxylic acid anhydride and polyamine material and further reacting this reaction product with organic dianhydride, aliphatically unsaturated organic anhydride and polyamine including polymethylene polyaniline. The polyamic acid is cured to provide the final polyamideimide which is useful for coating, adhesive, laminating, molding and other fabrications.

United States Patent 1 Hoback et al.

1 1 Jan. 30,1973

[54] POLYAMIDEIMIDES {75] Inventors: John T. Hoback; Fred F. l-lolub,

, both of Schenectady, NY.

[73] Assignee: General Electric Schenectady, NY.

22 Filed: Aug. 11,1971

21 App1.No.: 171,012

Company,

[52] US. Cl. ..260/78 TF, 117/132 13, 117/161 P, 260/32.8 M, 260/33.4 P,260/33.6 R, 260/47 CP, 260/6578 UA 3,575,924 4/1971 Bargain ..260/78 X3,576,691 4/1971 Meyers ..260/78 X 3,652,511 3/1972 Vincent et a1...260/78 3,661,852 5/1972 Flowers et a1. ..260/78 X 3,678,015 7/1972Holub et al ..260/78 Primary Examiner1-loward E. Schain Attorney-Howardl. Schlansker et a1.

[57] ABSTRACT New and useful polyamideimides and their precursorpolyamic acids are provided. The polyamic acid is prepared by reactingaliphatic diacid, tricarboxylic acid anhydride and polyamine materialand further reacting this reaction product with organic dianhydride,aliphatically unsaturated organic anhydride and polyamine includingpolymethylene polyaniline. The polyamic acid is cured to provide thefinal I polyamideimide which is useful for coating, adhesive,

laminating, molding and other fabrications.-

5 Claims, No Drawings POLYAMIDEIMIDES This invention relates to new anduseful polyamideimides and their precursor polyamic acids. Moreparticularly, the invention relates to polyamic acids which are preparedby reacting aliphatic diacid with tricarboxylic anhydride and polyaminematerial and further reacting this reaction product with organicdianhydride, aliphatically unsaturated organic anhydride andpolymethylene polyaniline, the polyamideimide being obtained by curingthe polyamic acid.

The use of polyamideimides as high temperature-resistant coating andelectrical insulating materials is well known, such compositions beingshown, for example, in US. Pat. Nos. 3,179,635; 3,471,444; 3,554,984;3,555,113; 3,562,217 and 3,576,691, among others. However, despite theavailability of such materials, there continues a search for new anduseful polyamideimides and their precursor polyamic acids which can bereadily prepared, applied to substrates or otherwise easily used andcured to provide coatings and the like having good flexibilityresistance to abrasion, good electrical qualities, and generally hightemperature-resistant characteristics.

it is a primary object of this invention to provide new and improvedpolyamic acids and polyamideimides. According to the invention, thepolyamic acid is prepared by first reacting in a relatively inexpensivesolvent aliphatic diacid, tricarboxylic acid anhydride and polyaminematerial, this first reaction product then being reacted with organicdianhydride, aliphatically unsaturated organic anhydride and polyamine,including polymethylene polyaniline to provide polyamic acid which iscured in the usual manner to the final polyamideimide resin state.Generally speaking, in the first reaction, one mole of acid material isused for each two moles of polyamine material, these amounts beingvariable by about fifteen mole percent. Up to about 95 mole percent ofthe diacid is replaced with an equivalent amount of tricarboxylic acidanhydride or ester. In the second reaction, there is reacted with thefirst reaction product plus an amount of polyamine equivalent to fivemole percent of the first reaction product an equivalent amount ofdianhydride and aliphatically unsaturated anhydride. At least fiveequivalent percent of the polyamine added in the second reaction ispolymethylene dianiline.

Those features of the invention which are believed to be novel are setforth with particularity in the claims appended hereto. The inventionwill, however, be better understood and further objects and advantagesthereof appreciated from a consideration of the following description.

As pointed out above, a drawback of many of the prior art materials ofthis general type has been that they require the use of relativelyexpensive solvents such as N-methylpyrrolidone, dimethylacetamide,pyridine, n-methyl-caprolactam, dimethyl sulfoxide, and the like. Whilethe present reactions can be carried out using such solvents, it is oneof the advantages of the present invention that relatively inexpensivesolvents can be used. For example, cresylic acids which are generally amixture of ortho-, meta-, and paracresol can be used as can such othermaterials such as cyclohexanone, acetophenone, and the like. Also usefulin connection with the present invention are what are so-called highboiling hydrocarbon solvents, such materials including, among others,Solvesso which is a mixture of mono-, diand trialkyl (primarily methyl)benzenes having a flash point of about 1 13 F and a distillation rangeof from about 318 to 352 F, such solvent being made by the Humble OilCompany. Another solvent useful in the present connection is Humble 670solvent, a mixture of mon'o-, di-, and trialkyl (primarily methyl)benzenes having a gravity API 60 F of 31.6 percent, a specific gravityof 60 F of 0.8676, a mixed aniline point of 1 1 F and a distillationrange of about 288to 346 F.

The aliphatic diacids useful in the present connection can be expressedby the formula I HOOC R COOH where R is an iiiiiiiiiifdEEEAEBEEQ,substituted or unsubstituted, aliphatic group containing from about oneto 40 carbon atoms. Among such diacids are oxalic, maleic, succinic,glutaric, adipic, pimelic, suberic, azelaic, sebacic and dodecanedioicacids, as well as unsaturated acids falling within the above formulaincluding maleic and fumaric acids, among others. Mixtures can, ofcourse, be used. A dibasic acid having a chain thirty-six carbons longis Emery Industries, 1nc.3713-R Dimer Acid. Others will occur to thoseskilled in the art.

Up to about 50, preferably up to about 20, equivalent percent of thealiphatic diacid can be substituted with aromatic diacids, typical ofwhich are terephthalic and isophthalic acids as well as aromaticanhydrides. Thetricarboxylic acid anhydride can be expressed by thefollowing formula:

where R is a trivalent organic radical. Among such materials which willoccur to those skilled in the art are trimellitic anhydride;2,6,7-naphthalene tricarboxylic anhydride, 3,3',4-diphenyl tricarboxylicanhydride; 3,3,4-benzophenone tricarboxylic anhydride; 1,3,4-cyclopentane tetracarboxylic anhydride; 2,2',3-diphenyl tricarboxylicanhydride; diphenyl sulfone-3,3',4- tricarboxylic anhydride; diphenylisopropylidene- 3,3',4-tricarboxylic anhydride; 3,4,l0-propylenetricarboxylic anhydride; 3,4-dicarboxyphenyl-3-carboxyphenyl etheranhydride; ethylene tricarboxylic anhydride; l,2,5-naphthalenetricarboxylic anhydride, etc. Also useful are the corresponding acids ofsuch anhydrides. Where diacids are mentioned, such substitutions will beunderstood to be included.

In lieu of the tricarboxylic acid anhydride material, there can be usedin whole or in part the reaction product of such materials with glycolhaving the formula where R is hydrogen or a monovalent hydrocarbonradical, for example, alkyl radicals (e.g., methyl, ethyl, propyl,isopropyl, butyl, decyl, etc.), aryl radicals (e.g., phenyl, naphthyl,biphenyl, tolyl, xylyl, etc.), aralkyl radicals (e.g., benzyl,ethylphenyl, etc.), cycloaliphatic radicals (e.g., cyclopentyl,cyclohexyl, etc.), as well as monovalent hydrocarbon radicals containinginert substituents thereon, such as halogen (chlorine, bromine,fluorine, etc.). It will be understood that where more than one R" isused, they may be alike or different. R' can be selected from the groupconsisting of alkylene and alkylidene residues such as methylene,ethylene, propylene, propylidene, isopropylidene, butylene, butylidene,isobutylidene, amylene, isoamylene, amylidene, isoamylidene, etc. R' canalso be a silane radical or can be polyalkoxy such as polyethoxy,polypropoxy, polythioethoxy, polybutoxy, polyphen- 'ylethoxy, orpolyorganosiloxy, for example, polydimethylsiloxy, polydiphenylsiloxy,

. polymethylphenylsiloxy, etc. R can also consist of two or morealkylene or alkylidene groups such as above, separated by an aromaticgroup, a tertiary amino group, an ether group, a carbonyl group, asilane group, or by a sulfur containing group such as sulfide,sulfoxide, sulfone, etc. R' may also be a glycol dibasic acid esterresidue derived from, for example, dibasic acids such as adipic,azelaic, sebacic, isophthalic, terephthalic and glycols such as havebeen disclosed above. Other groupings which can be represented by R'will occur to those skilled in the art. The ester residue can bepolymeric or monomeric. The subscript p can be a whole number includingzero. The subscript q is an integer which may be varied as desired andR, where q is more than 1, may be like or different radicals. It isunderstood, of course, that mixtures of different glycols may be usedand where glycol is mentioned, such mixtures are considered to beincluded.

Such reaction products of tricarboxylic acid anhydride and glycol can beexpressed by the formula i a i where R is a divalent hydrocarbonradical, preferably containing from two to 12 carbon atoms.

The polyamines useful in connection with the present invention are wellknown and can be expressed by the formula v x R 4 (NH,),,

3-methylheptamethylene diamine 4,4'-dimethylheptamethylene diamine 2,1l-diamino-dodecane l ,2-bis-( 3-amino-propoxy )ethane 2,2-dimethylpropylene diamine 3-methoxy-hexamethylene diamine 2,5-dimethylhexamethylene diamine 2,5-dimethylheptamethylene diamineS-methylnonamethylene diamine 1,4-diamino-cyclo-hexane l ,1Z-diamino-octadecane 2,5-diamino-l ,3 ,4-oxadiazole 2 2)a z)z 2)a 2 2z)a :)a 2 z z)a a)( z)a z meta-phenylene diamine para-phenylene diamine4,4'-diamino-diphenyl propane 4,4'-diamino-diphenyl methane benzidine4,4'-diamino-diphenyl sulfide 4,4 '-diamino-diphenyl sulfone 3 ,3'-diamino-diphenyl sulfone 4,4'-diamino-diphenyl ether2,6-diamino-pyridine bis(4-amino-phenyl)diethyl silanebis(4-amino-phenyl)diphenyl silane bis(4-amino-phenyl)phosphine oxide4,4-diaminobenzophenone bis(4-amino-phenyl)-N-methylaminebis(4-aminobutyl)tetramethyldisiloxane 1 ,S-diaminonaphthaIene 3 ,3'-dimethyl-4,4'-diamino-biphenyl 3,3 '-dimethoxy benzidine2,4-bis(beta-amino-t-butyl)toluene toluene diamine bis(parabeta-amino-t-butyl-phenyl)ether para-bis(2-methyl-4-amino-pentyl)benzenepara-bis( l ,l-dimethyl-5-amino-pentyl)benzene m-xylylene diaminepolymethylene polyaniline of formula mil 1-1-? V. Lb J where n is from0.1 to 10.

Dianhydrides expressed by the formula Rn A 3 ,3 ,4 ,4 '-diphenyltetracarboxylic dianhydride 1,2,5 ,6-n aphthalene tetracarboxylicdianhydride 2,2' ,3 ,3 -diphenyl tetracarboxylic dianhydride 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride bis(3,4-dicarboxyphenyl)sulfonedianhydride 3,4,9,1 O-perylene tetracarboxylic dianhydride bis( 3,4-dicarboxyphenyl)ether dianhydride ethylene tetracarboxylicdianhydride naphthalene-1,2,4,5-tetracarboxylic dianhydridenaphthalene-1,4,5 ,S-tetracarboxylicdecahydronaphthalene-l,4,5,8-tetracarboxylic dianhydride 4,8-dimethyl-l,2,3,5 ,6,7-hexahydronaphthalene- 1,2,5 ,6-tetracarboxylic dianhydride2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride 2,3,6,7-tetrachloronaphthalene-1,4,5 ,S-tetracarboxylic dianhydridephenanthrene-l ,8,9,10-tetracarboxylic dianhydride cyclopentane-l,2,3,4-tetracarboxylic dianhydride pyrrolidine-2,3,4,5-tetracarboxylicdianhydride pyrazine- 2,3,5,6-tetracarboxylic dianhydride2,2-bis(2,3-dicarboxypheny1)propane dianhydridel,l-bis(2,3-dicarboxyphenyl)ethane dianhydride1,1-bis(3,4-dicarboxyphenyl)ethane dianhydridebis(2,3-dicarboxyphenyl)methane dianhydridebis(3,4-dicarboxyphenyl)methane dianhydridebis(3,4-dicarboxyphenyl)sulfone dianhydride benzene-1,2,3,4-tetracarboxylic dianhydride 1,2,3,4-butane tetracarboxylicdianhydride thiophene-2,3,4,5-tetracarboxylic dianhydride 3,3',4,4'-diphenyltetracarboxylic dianhydride 3 ,4,3 ,4'-benzophenonetetracarboxylic dianhydride azobenzene tetracarboxylic dianhydride2,3,4,5-tetrahydrofuran dianhydridep-phenylenebis(trimellitate)anhydride1,2-ethylenebis(trimellitate)anhydride 2,2-propanebis(p-phenylenetrimellitate )anhydride 4,4'[p-phenylenebis(phenylimino)carbonyldiphthalic] anhydride 4,4'-diphenylmethanebis(trimellitamide)anhydrideand mixtures thereof. The aliphatically unsaturated organic anhydridesuseful in the present respect can be expressed by the formula where R isan aliphatically unsaturated divalent organic radical selected fromdianhydride where Y is a radical selected from hydrogen, lower alkyl,halogen, or mixtures thereof, such as chloromethyl, ethyl, propyl,bromo, and the like.

The following examples will illustrate the practice of the invention, itbeing understood that they are not to be taken as limiting in any way.All parts are by weight.

EXAMPLE 1 There were mixed together in a resin kettle equipped with astirrer, a Dean Stark trap with condenser, and a thermometer 198.26parts p,p'-methylene dianiline, 62.79 parts azelaic acid, 64.17 partstrimellitic anhydride and 36.l3 parts cresol, about 39 parts of xylenebeing placed in the Dean Stark trap to assist in removing water. Themixture was heated at 190 C until the water stopped azeotropicallydistilling, 21 parts of water being removed along with the xylene. Tothis product there were added about 387.2 parts cresol to make asolution containing 43.5 percent solids.

Shown in Table 1 below are various reactions carried out using theindicated amounts of the product of Example l, all reactions beingcarried out in mixtures containing 20 percent solids, the mixture beingheated from about to C.

TABLE I Ex. Added Ex. 1 Curithane Nadic BTDA Cresol Ex. 1 Solids 103 MAAnhydride la 35.7 18.66 (8.11) 0.206 0.32 2.9 lb 33.9 v 16.79 (7.3) 0.410.65 2.6 1c 32.2 14.7 (6.39) 0.61 0.97 2.2 1d 33.8 16.8 (7.3) 0.41 0.322.9 1e 33.8 16.8 (7.3) 0.41 0.97 2.2 11 33.9 16.3 (7.3) 0.4 0.4 0.97 2.6

MA=maleic anhydride BTDA=benmphenone dianhydride All of the reactionproducts of Examples la through 11' above coated smoothly on aluminum toprovide a high temperature-resistant film after curing for ten minutesat 250 C.

EXAMPLE 2 There were charged into a resin kettle equipped with astirrer, a Dean Stark trap with condenser and a thermometer 198.26 partsp,p'-methylenedianiline, 62.79 parts azelaic acid, 136.94 parts4,4'-ethylene-bis-anhydro-trimellitate (TMAEG) and 43.32 parts cresol.About 39 parts xylene were placed in the trap to help remove water. Themixture was heated at C until the water stopped azeotropicallydistilling. The theoretical amount of water was removed along with thexylene. About 517 parts of cresol were added to this product to make asolution containing 40 percent solids.

Shown in Table II below are various reactions carried out using theindicated amounts of the product of Example 2 along with the otherindicated materials. All of the following reactions were carried out inmixtures containing 20 percent solids in a flask equipped with astirrer, thermometer and a condenser with N bypass. After heating from80 to 1 10 C over 510 minutes, all gave a good flexible film on aluminumwith curing to 20 minutes at 250 C.

EXAMPLE 5 There were charged into a resin kettle equipped as in Example2, 108.14 parts meta-phenylene diamine,

TABLE I1 Curt- Cut- Added Ex. 2 thane thru, Example cresol Ex. 2 solids#103 PMDA BTDA MA 0.

2a 48. 44 22. 43 8. 97 0. 41 2. 6 0. 4 320 2b 43. 94 22. 43 8. 97 0.41 1. 74 0. 4 350 2c 42. 57 19. 8 7. 92 0. 61 1. 96 0. 4 385PMDA=pyrome11it1c dianhydride.

EXAMPLE 3 azfisiafis azelaic acid, 136.94 parts TM A -Eand There werecharged into a resin kettle equipped as in Example 2, 198.26 partsp,p-methylene dianiline,

136.94 parts TMA-EG, 21.6 parts isophthalic acid and 38.35 parts azelaicacid. About 39 parts xylene were placed in the trap to help remove thewater. The mixture was heated at 190 C until the water stoppedazeotropically distilling. The theoretical amount of water was removedalong with the xylene. About 513 parts cresol-were added to this productto make a solution containing 40 percent solids.

Shown in Table [11 below arecertain reactions carried out using theproduct of Example 3. All of the following reactions were carried out inmixtures containing about 20 percent solids in a flask equipped with astirrer, thermometer and a condenser with N bypass. W

33.31 parts cresol. About 39 parts xylene were placed in the trap tohelp remove the water. The mixture was heated at 190 C until the waterstopped azeotropically distilling. The theoretical amount of water wasremoved along with the xylene. About 392 parts of cresol were added tothis product to make a solution containing 40 percent solids.

Shown in Table V below are certain reactions carried out using theproduct of Example 5. All of the reactions were carried out in mixturescontaining about 20 percent solids in a flask equipped with a stirrer,thermometer and a condenser with N bypass. After heating from 80 to 110C over 5-10 minutes, all gave a good flexible film on aluminum withcuring 10 to 20 minutes at 250 C.

TABLE V Curi- Cut- Added Ex. 5 thane thru, Example Cresol Ex. 5 solids#103 PMDA BTDA MA C.

58 40. 68 17. O3 6. 81. O. 41 2. 6 0. 4 340 5b 36. 3B 17. 03 6. 81 0.41 1. 74 0. 4 385 After heating from 80 t o 1 10 C over 5-10 minutes,all A 6 M gave a good flexible film on aluminum with curing There werecharged into a resin kettle equipped as in Example 2, 116.2 partshexamethylene diamine, 62.79 parts azelaic acid, 136.94 parts TMA-EG and34.20

' parts cresol. About 39 parts xylene were placed in the trap to helpremove the water. The mixture was heated at 190 C until the waterstopped azeotropically distilling. The theoretical amount of water wasremoved along with the xylene. About 403 parts of cresol were added tothis product to make a solution containing 40 percent solids.

Shown in Table IV below are certain reactions carried out using theproduct of Example 4. All of the following reactions were carried out inmixtures containing about 20"percent solids in a flask equipped with astirrer, thermometer and a condenser with N bypass. After heating from80 to 1 10 C over 5-10 minutes, all gave a good flexible film onaluminum with curing 10 to 20 minutes at 250C.

There were charged into a resin kettle equipped as in Example 2, 198.26parts p,p'-methylene dianiline, 99.64 parts azelaic acid, 53.3 partsTMA-EG and 38.16 parts cresol. About 39 parts xylene were placed in thetrap to help remove the water. The mixture was heated to 190 C until thewater stopped azeotropically. distilling. The theoretical amount ofwater was removed along with-the xylene. About 452 parts of cresol wereadded to this product to make a solution containing 40 percent solids.

Shown in TabIe VT below 'aifiznamiea'cubns car'- ried out using theproduct of Example 6. All of the following reactions were carried out inmixtures containing about 20 percent solids in a flask equipped with astirrer, thermometer and a condenser with N, bypass.

After heating from to 1 10 C over 5-10 minutes, all.

gave a good flexible film on aluminum with curing 10 to 20 minutes at250 C.

There are provided, then, by the present invention new and usefulpolyamideimide materials and their precursor polyamic acids which areuseful for providing films for electrical insulation and other purposes.They are also useful for coating substrates in general and are useful asadhesives in the preparation of laminates. In the divided state they canbe usedfor molding purposes either unfilled or filled with theusualfillers.

TABLE VI 'W d Curi- Out- Added Ex. 6 thane thru. Example Cresol Ex. 6solids #103 PMDA BTDA MA C,

What we clai nias new'ahaaesir'e to secureby Letters Patent of theUnited States is:

l. The product of reaction of (I) the reaction product of (a) aliphaticdiacid, (b) material selected from tricarboxylic acid anhydride andesters of such anhydride, 'and (c) polyamine material and (11) organicdianhydride, aliphatically unsaturated organic anhydride, and poiyamineincluding that having the for-

1. The product of reaction of (I) the reaction product of (a) aliphaticdiacid, (b) material selected from tricarboxylic acid anhydride andesters of such anhydride, and (c) polyamine material and (II) organicDianhydride, aliphatically unsaturated organic anhydride, and polyamineincluding that having the formula
 2. A product as in claim 1 where aportion of said aliphatic diacid is substituted with material selectedfrom (a) aromatic acid and anhydride and mixtures thereof containing atleast two groups selected from carboxyl and anhydride groups and (b)aliphatic anhydride.
 3. A coating composition of the product of claim 1in a compatible solvent.
 4. A substrate coated with the cured product ofclaim 1.